The miscibility and morphology of poly(caprolactone) (PCL) and poly (4-vinylphenol) (PVPh) blends were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and 13C solid state nuclear magnetic resonance (NMR) spectroscopy. The DSC results indicate that PCL is miscible with PVPh. FTIR studies reveal that hydrogen bonding exists between the hydroxyl groups of PVPh and the carbonyl groups of PCL. 13C cross polarization (CP)/magic angle spinning (MAS)/dipolar decoupling (DD) spectra of the blends show a 1 ppm downfield shifting of 13C resonance of PVPh hydroxyl-substituted carbons and PCL carbonyl carbons with increasing PCL content. Both FTIR and NMR give evidence of inter-molecular hydrogen bonding within the blends. The proton spin-lattice relaxation in the laboratory frame, T1(H), and in the rotating frame, T1ρ(H), were studied as a function of the blend composition. The T1(H) results are in good agreement with thermal analysis; i.e. the blends are completely homogeneous on the scale of 50-80 nm. The T1ρ(H) results indicate that PCL in the blends has both crystalline and amorphous phases. The amorphous PCL phase is miscible with PVPh, but the PCL crystal domain size is probably larger than the spin-diffusion path length within the T1ρ(H) time-frame, i.e. larger than 2-4 nm. The mobility differences between the crystalline and amorphous phases of PCL are clearly visible from the T1ρ(H) data. 相似文献
The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter Xij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χinter and the free volume term χfree. Both the temperature and copolymer composition dependences of χinter and χfree were estimated by calculations using the equation of state parameters. There exists a region in which χinter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χinter; it is caused by the free volume contribution, χfree. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory. 相似文献
An approach to the analysis of 55 possible nonconjugated positional isomers of octadecadienoic acid is described and tested
with mixtures of individual synthetic methyl esters. In the first example, by ozonolysis a sevencomponent mixture consisting
ofcis,cis 5,12-, 6,10-, 6,11-, 6,12-, 7,12-, 8,12-, and 9,12-octadecadienoates was converted to aldehydes, aldehyde-esters and dialdehydes.
These fragments were separated on a 50 m×0.2 mm free fatty acid phase (FFAP) vitreous silica capillary column. Equations for
an arbitrarily restricted 12×15 matrix of linear simultaneous equations and a computer solution of the matrix provided the
composition of the initial methyl octadecadienoate mixture. The power and significance of this method became apparent with
the observation that only two of the seven isomers in the known mixture were resolved as single peaks by state-of-the-art
capillary gas chromatography, but all seven were identified and estimated with acceptable error by the ozonolysis-capillary
gas chromatography-computer procedure. In a generalized approach to the analysis of the 55 possible nonconjugated isomers,
a computer program selects the appropriate matrix of linear simultaneous equations based on the aldehyde data supplied by
the analyst. Twenty of 21 combinations of seven isomeric esters taken five at a time have been analyzed to assess the efficiency
of the method. To illustrate applicability at this stage of development, the method has been used to analyze the diene products
of the hydrazine reduction of γ-linolenic acid and the diene products from the biological desaturation of isomeric monoenes.
The possibility of distinguishing geometric and positional isomers of 18∶2 has been opened by the observed separation ofcis-andtrans-unsaturated aldehydes and aldehyde-esters.
Presented in part at the 16th World Congress of the International Society for Fat Research, October 4–7, 1983, in Budapest,
Hungary, and at the American Oil Chemists' Society Meeting, May 15, 1986, in Honolulu, Hawaii. 相似文献
We present two methods for designing amino acid sequences ofproteins that will fold to have good hydrophobic cores. Giventhe coordinates of the desired target protein or polymer structure,the methods generate sequences of hydrophobic (H) and polar(P) monomers that are intended to fold to these structures.One method designs hydrophobic inside, polar outside; the otherminimizes an energy function in a sequence evolution process.The sequences generated by these methods agree at the levelof 6080% of the sequence positions in 20 proteins inthe Protein Data Bank. A major challenge in protein design isto create sequences that can fold uniquely, i.e. to a singleconformation rather than to many. While an earlier lattice-basedsequence evolution method was shown not to design unique folders,our method generates unique folders in lattice model tests.These methods may also be useful in designing other types offoldable polymer not based on amino acids 相似文献
The hydrogen bonding, miscibility, crystallization, and thermal stability of poly(3‐hydroxybutyrate) (PHB)/4‐tert‐butylphenol (BOH) blends and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)]/BOH blends were investigated by Fourier transform infrared (FTIR) spectroscopy, solid‐state13C‐NMR, differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), and thermogravimetric analysis. The results of FTIR spectroscopy and solid‐state13C‐NMR show that intermolecular hydrogen bonds existed between the two components in the blends and that the interaction was caused by the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of BOH. With increasing BOH content, the chain mobility of both the PHB and P(3HB‐3HHx) components was improved. After the samples were quenched, the detected single glass‐transition temperatures decreased with composition, indicating that both PHB/BOH and P(3HB‐3HHx)/BOH were miscible blends in the melt. Moreover, as BOH content increased, the melting temperatures of PHB and P(3HB‐3HHx) clearly decreased, which implied that their crystallization was suppressed by the addition of BOH. Although the crystallinity of PHB and P(3HB‐3HHx) components decreased with increasing BOH content in the blends, their crystal structures were hardly affected after they were blended with BOH, which was further proven by WAXD results. In addition, the thermal stability of PHB was improved by a smaller amount of BOH. 相似文献
The effects of platinum (Pt) and silver (Ag) metallisation in the photocatalytic oxidation of resorcinol at pH 3 ± 0.5 have been investigated. The photocatalytic degradation of resorcinol was significantly improved by Pt/TiO2, while the presence of Ag/TiO2 enhanced the initial photocatalytic degradation rate of resorcinol slightly. Likewise, the photocatalytic mineralisation of resorcinol continued to be enhanced by Pt/TiO2, but it was retarded when Ag/TiO2 was used.
The function of Pt and Ag deposits on the surface of TiO2 has been found to be markedly influenced by the interaction of resorcinol and its degradation products with the metal deposits. The presence of Pt or Ag on the surface of TiO2 altered the distribution of degradation products of resorcinol as well as the production of photoactive species for the photocatalytic oxidation of resorcinol. The X-ray photoelectron spectroscopy (XPS), zeta potential and transmission electron microscopy (TEM) analyses have indicated that the contrasting effect of Pt and Ag deposits were governed by the oxidation states and the catalytic property of metal deposits. In addition to that, it has been found that the roles of metal deposits are specific and should not be generalised. 相似文献
Some stereoblind observers do not perceive depth of 3D stimuli that depends on binocular disparity. These individuals, who have no disabilities, comprise over 5% of the general population. In addition, 17–30% of nonstereoblind young and young–middle people do not use disparity information in certain 3D environments, a phenomenon known as pseudo‐stereoblindness. This study aimed to investigate the relationship between aging and the proportion of pseudo‐stereoblindness in the general population. In an experiment, 134 nonstereoblind participants, ranging in age from 17 to 83 years, judged subjective depth of 3D stimuli containing binocular disparity and pictorial depth cues. Results showed that the proportion of pseudo‐stereoblindness among young (17–24 years old) and young–middle aged observers (25–39 years old) was 29%, in both cases. However, the proportion of pseudo‐stereoblind observers increased in older populations: 65% and 82% in the middle (40–54 years old) and senior (55–83 years old) age groups, respectively. These results suggest that a number of people, especially in elderly populations, have trouble perceiving depth from binocular disparity in 3D graphic contents despite their essential ability to use disparity information. 相似文献